JP4571790B2 - Long fiber reinforced resin pellets and molded articles thereof - Google Patents
Long fiber reinforced resin pellets and molded articles thereof Download PDFInfo
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- JP4571790B2 JP4571790B2 JP2003319606A JP2003319606A JP4571790B2 JP 4571790 B2 JP4571790 B2 JP 4571790B2 JP 2003319606 A JP2003319606 A JP 2003319606A JP 2003319606 A JP2003319606 A JP 2003319606A JP 4571790 B2 JP4571790 B2 JP 4571790B2
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- 229920005989 resin Polymers 0.000 title claims description 102
- 239000011347 resin Substances 0.000 title claims description 102
- 239000000835 fiber Substances 0.000 title claims description 101
- 239000008188 pellet Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 claims description 61
- 229920001155 polypropylene Polymers 0.000 claims description 43
- -1 polypropylene Polymers 0.000 claims description 35
- 238000002425 crystallisation Methods 0.000 claims description 29
- 230000008025 crystallization Effects 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 229920001384 propylene homopolymer Polymers 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 13
- 230000000704 physical effect Effects 0.000 claims description 13
- 229920000098 polyolefin Polymers 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000004513 sizing Methods 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 238000000691 measurement method Methods 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005481 NMR spectroscopy Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 26
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Description
本発明は、長繊維強化ポリプロピレン系樹脂ペレット、長繊維強化樹脂ブレンド組成物及びそれらを成形してなる成形体に関する。 The present invention relates to a long fiber reinforced polypropylene resin pellet, a long fiber reinforced resin blend composition, and a molded body formed by molding them.
従来、繊維強化樹脂組成物は、金属やエンジニアリングプラスチックの代替材料としての用途が知られている。しかしながら、従来の繊維強化樹脂組成物は金属やエンジニアリングプラスチックに比べて強度がやや不足している為、その代替範囲は限られていた。 Conventionally, a fiber reinforced resin composition is known to be used as an alternative material for metals and engineering plastics. However, since the conventional fiber reinforced resin composition is slightly lacking in strength compared to metals and engineering plastics, its range of substitution has been limited.
一般に、ポリプロピレンなどのオレフィン系樹脂は非晶部量などが同一であれば、結晶化温度（Ｔｃ）が高いほど引張り破壊強度や曲げ強さが高いと言われている。それ故、短繊維強化ポリプロピレン（強化用繊維のチョップドストランドとポリプロピレン系樹脂とを混練して作られ、重量平均繊維長さが１ｍｍ以下（一般に０．３〜０．５ｍｍ）のもの）を含むオレフィン系複合材料においては、強度を向上させる為に樹脂部の結晶化温度を高めることが一般的である。その為、長繊維強化樹脂においても、より結晶化温度の高い樹脂を選択するか、造核剤などで結晶化温度を上げた樹脂を使用していた。特許文献１には、結晶化温度が向上したことにより強度が優れた長繊維強化ポリオレフィンが開示されている。特許文献２にも、結晶化温度を高めることで剛性を高めることが開示されている。
特許文献３にはサイジング剤中に造核剤を加えることで、トランスクリスタル層を成長させる方法が開示されている。しかし、この方法では、射出成形した場合に造核剤が樹脂中に分散してしまい，所望の物性が得られない可能性がある。
Generally, olefinic resins such as polypropylene are said to have higher tensile fracture strength and bending strength as the crystallization temperature (Tc) is higher if the amount of amorphous part is the same. Therefore, olefins containing short fiber reinforced polypropylene (made by kneading chopped strands of reinforcing fibers and polypropylene resin and having a weight average fiber length of 1 mm or less (generally 0.3 to 0.5 mm)) In the system composite material, it is general to increase the crystallization temperature of the resin portion in order to improve the strength. For this reason, among the long fiber reinforced resins, a resin having a higher crystallization temperature is selected, or a resin whose crystallization temperature is increased with a nucleating agent or the like is used. Patent Document 1 discloses a long fiber reinforced polyolefin having excellent strength due to an improved crystallization temperature. Patent Document 2 also discloses that the rigidity is increased by increasing the crystallization temperature.
Patent Document 3 discloses a method of growing a transcrystal layer by adding a nucleating agent to a sizing agent. However, in this method, when injection molding is performed, the nucleating agent is dispersed in the resin, and the desired physical properties may not be obtained.
しかしながら、長繊維強化樹脂においては、結晶化温度の高い樹脂を用いても、その強度向上には限界が有った。
本発明は、上記事情に鑑みなされたものであり、長繊維強化樹脂成形体の強度をさらに向上させることができる、長繊維強化ポリプロピレン系樹脂ペレット及び長繊維強化樹脂ブレンド組成物を提供することを目的とする。
However, in the long fiber reinforced resin, even if a resin having a high crystallization temperature is used, there is a limit in improving the strength.
The present invention has been made in view of the above circumstances, and provides a long fiber reinforced polypropylene resin pellet and a long fiber reinforced resin blend composition that can further improve the strength of a long fiber reinforced resin molded article. Objective.
上記目的を達成するため、本発明者は鋭意研究を重ねた結果、一般のポリプロピレン系複合材料では、結晶化温度が高いものほど強度は向上するが、長繊維強化ポリプロピレン系樹脂においては、結晶化温度が一定の温度以下になると、強度を含む物性が飛躍的に向上することを見出し、本発明を完成させた。 In order to achieve the above object, the present inventor has conducted extensive research. As a result, in general polypropylene composite materials, the higher the crystallization temperature, the higher the strength, but in the long fiber reinforced polypropylene resin, crystallization occurs. It has been found that the physical properties including strength are dramatically improved when the temperature is below a certain temperature, and the present invention has been completed.
物性が飛躍的に向上する理由は完全には解明されていないが次のように考えられる。プロピレン重合体などの結晶性樹脂においては、特定の温度で、強化用繊維が結晶核となり繊維部からトランスクリスタルと呼ばれる結晶層が発現する。従来の結晶化温度の高い樹脂を用いると、樹脂部の結晶化温度がトランスクリスタルが発現する温度より高く、冷却過程において樹脂部の結晶化が先行し、繊維部からのトランスクリスタル層が十分に成長できず、強化繊維界面の補強効果が損なわれると考えられる。 The reason for the dramatic improvement in physical properties has not been fully elucidated, but is thought to be as follows. In a crystalline resin such as a propylene polymer, at a specific temperature, a reinforcing fiber becomes a crystal nucleus and a crystal layer called a transcrystal appears from the fiber portion. If a conventional resin having a high crystallization temperature is used, the crystallization temperature of the resin part is higher than the temperature at which the transcrystal appears, the crystallization of the resin part precedes in the cooling process, and the transcrystal layer from the fiber part is sufficient. It cannot be grown, and the reinforcing effect at the reinforcing fiber interface is considered to be impaired.
そこで、本発明においては、樹脂部の結晶化温度がトランスクリスタル層発現温度より低い樹脂を用いることにより、長繊維強化樹脂成形体の強度を飛躍的に向上させ、より高い強度が要求される用途への適用を可能とした。 Therefore, in the present invention, by using a resin whose crystallization temperature of the resin part is lower than the expression temperature of the transcrystal layer, the strength of the long fiber reinforced resin molded product is dramatically improved and a higher strength is required. It was possible to apply to.
本発明の第１の態様によれば、示差走査熱量計（ＤＳＣ）測定法で測定した樹脂マトリックス部の結晶化温度（Ｔｃ）が１０５〜１２０℃の長繊維強化ポリプロピレン系樹脂ペレットが提供される。 According to the first aspect of the present invention, a long fiber reinforced polypropylene resin pellet having a crystallization temperature (Tc) of 105 to 120 ° C. of a resin matrix portion measured by a differential scanning calorimeter (DSC) measurement method is provided. .
本発明の第２の態様によれば、上記本発明の第１の態様の長繊維強化ポリプロピレン系樹脂ペレットと、（Ｄ）プロピレン単独重合体及び／又はプロピレン系ブロック共重合体とをブレンドしてなる長繊維強化樹脂ブレンド組成物が提供される。 According to the second aspect of the present invention, the long fiber reinforced polypropylene resin pellets of the first aspect of the present invention and (D) a propylene homopolymer and / or a propylene block copolymer are blended. A long fiber reinforced resin blend composition is provided.
本発明の第３の態様によれば、上記本発明の第１の態様の長繊維強化ポリプロピレン系樹脂ペレット又は上記本発明の第２の態様の長繊維強化樹脂ブレンド組成物を成形してなる成形体であって、成形後に残存する繊維の重量平均繊維長が１ｍｍ以上であることを特徴とする成形体が提供される。成形体の例として、重量１ｋｇ以上の自動車のフロントエンドなどが挙げられる。 According to the third aspect of the present invention, molding is performed by molding the long fiber reinforced polypropylene resin pellet of the first aspect of the present invention or the long fiber reinforced resin blend composition of the second aspect of the present invention. A molded body is provided, wherein a weight average fiber length of fibers remaining after molding is 1 mm or more. Examples of the molded body include a front end of an automobile having a weight of 1 kg or more.
本発明によれば、長繊維強化樹脂成形体の強度をさらに向上させることができる、長繊維強化ポリプロピレン系樹脂ペレット及び長繊維強化樹脂ブレンド組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the long fiber reinforced polypropylene resin pellet and long fiber reinforced resin blend composition which can further improve the intensity | strength of a long fiber reinforced resin molded object are provided.
以下、本発明を詳細に説明する。
本発明の第１の態様である長繊維強化ポリプロピレン系樹脂ペレット（以下、本発明のペレットという）は、示差走査熱量計（ＤＳＣ）測定法で測定した樹脂マトリックス部の結晶化温度（Ｔｃ）が１０５〜１２０℃、好ましくは１１０〜１１８℃、特に好ましくは１１３〜１１６℃であることを特徴とする。
Hereinafter, the present invention will be described in detail.
The long fiber reinforced polypropylene resin pellets (hereinafter referred to as pellets of the present invention), which is the first aspect of the present invention, have a crystallization temperature (Tc) of the resin matrix portion measured by a differential scanning calorimeter (DSC) measurement method. It is 105-120 degreeC, Preferably it is 110-118 degreeC, Most preferably, it is 113-116 degreeC, It is characterized by the above-mentioned.
樹脂マトリックス部の結晶化温度（Ｔｃ）が１０５℃未満のポリプロピレン系樹脂は剛性が低く、長繊維強化用には不向きである。Ｔｃが１２０℃を超えると、トランスクリスタル層が十分に成長しないため、強度が低下する。 Polypropylene resins having a resin matrix portion crystallization temperature (Tc) of less than 105 ° C. have low rigidity and are not suitable for reinforcing long fibers. When Tc exceeds 120 ° C., the transcrystal layer does not grow sufficiently, and the strength decreases.
本発明のペレットにおいては、長さが２〜２００ｍｍ、好ましくは４〜１２ｍｍ、特に好ましくは６〜９ｍｍの繊維が、ペレットの長手方向へ略平行に配列され、上記の樹脂マトリックスが、該繊維間に含浸されていることが好ましい。繊維がペレットの長手方向と略平行に配列することによって、
繊維長を比較的長く保った状態で、射出成形、押出成形等が可能であり、高剛性、高衝撃強度の成形品が得られるという効果が得られる。繊維をペレットの長手方向と略平行に配列するには、公知の引き抜き成形方法、例えば特開平１０−２６４１５２号公報に開示された方法で製造すればよい。
In the pellet of the present invention, fibers having a length of 2 to 200 mm, preferably 4 to 12 mm, particularly preferably 6 to 9 mm are arranged substantially parallel to the longitudinal direction of the pellet, and the resin matrix is formed between the fibers. Is preferably impregnated. By arranging the fibers substantially parallel to the longitudinal direction of the pellet,
Injection molding, extrusion molding and the like are possible with the fiber length kept relatively long, and an effect that a molded product having high rigidity and high impact strength can be obtained. In order to arrange the fibers substantially in parallel with the longitudinal direction of the pellet, the fibers may be manufactured by a known pultrusion method, for example, a method disclosed in JP-A-10-264152.
本発明のペレットは、カルボン酸化合物又はその誘導体を０．００２〜２質量％含有していることが好ましい。０．００２質量％未満では、ペレットの機械物性が十分に発現せず、２質量％を超えると、機械物性、耐熱性が低下する恐れがある。ここで、「カルボン酸化合物又はその誘導体」は、本発明のペレット中に必要に応じて用いられるカルボン酸又はカルボン酸無水物変性ポリオレフィンを製造するために用いられるものである。 The pellet of the present invention preferably contains 0.002 to 2% by mass of a carboxylic acid compound or a derivative thereof. If it is less than 0.002% by mass, the mechanical properties of the pellet are not sufficiently exhibited, and if it exceeds 2% by mass, the mechanical properties and heat resistance may be lowered. Here, the “carboxylic acid compound or derivative thereof” is used for producing a carboxylic acid or carboxylic anhydride-modified polyolefin used as necessary in the pellet of the present invention.
上記範囲の結晶化温度を有する本発明のペレットは、好ましくは、下記の組成を有する：
（Ａ）ＤＳＣ測定法で測定したＴｃが１０５〜１２０℃のポリプロピレン系樹脂 １０〜６９．９質量％、
（Ｂ）ＤＳＣ測定法で測定したＴｃが９０〜１２５℃のカルボン酸化合物又はその誘導体によって変性されたポリオレフィン（以下、酸変性ポリオレフィンという） ０．１〜２０質量％、及び
（Ｃ）カップリング剤及びフィルム・フォーマーを含む収束剤で処理された繊維径５〜２０μｍの繊維 ３０〜７０質量％。
The pellets of the present invention having a crystallization temperature in the above range preferably have the following composition:
(A) 10 to 69.9% by mass of a polypropylene resin having a Tc of 105 to 120 ° C. measured by DSC measurement method,
(B) 0.1 to 20% by mass of a polyolefin (hereinafter referred to as acid-modified polyolefin) modified with a carboxylic acid compound or derivative thereof having a Tc of 90 to 125 ° C. measured by DSC measurement method, and (C) a coupling agent And 30 to 70% by mass of fibers having a fiber diameter of 5 to 20 μm treated with a sizing agent including a film former.
上記（Ａ）成分のポリプロピレン系樹脂の結晶化温度（Ｔｃ）は、１０５〜１２０℃、好ましくは１１０〜１１８℃、特に好ましくは１１３〜１１６℃の範囲であることが必要である。Ｔｃが上記範囲でないと、樹脂マトリックス部のＴｃが目的とする１０５〜１２０℃の範囲にならない。（Ａ）成分が１０質量％未満であると、得られたペレットの流動性が著しく低下する恐れがあり、６９．９質量％を超えると、長繊維ガラス繊維マスターバッチとしての製造が難しくなる上、マスターバッチとしての実用性が劣ったものとなり、ガラス繊維量が任意のポリプロピレン系樹脂組成物の調整自由度が狭くなる。言い換えれば、ガラス繊維を多く含むペレットほど、任意のガラス繊維量のポリプロピレンペレットを調整できる。また、（Ｃ）成分は特に４０〜６０質量％が好ましい。 The crystallization temperature (Tc) of the polypropylene resin as the component (A) needs to be in the range of 105 to 120 ° C, preferably 110 to 118 ° C, and particularly preferably 113 to 116 ° C. If Tc is not in the above range, the Tc of the resin matrix portion does not fall within the target range of 105 to 120 ° C. When the component (A) is less than 10% by mass, the fluidity of the obtained pellet may be significantly reduced. When the component exceeds 69.9% by mass, it becomes difficult to produce a long fiber glass fiber master batch. The practicality as a masterbatch becomes inferior, and the degree of freedom of adjustment of the polypropylene resin composition having any glass fiber amount becomes narrow. In other words, polypropylene pellets having an arbitrary amount of glass fiber can be prepared as the pellet contains more glass fiber. Further, the component (C) is particularly preferably 40 to 60% by mass.
成分（Ａ）のポリプロピレン系樹脂は、下記物性を有するプロピレン単独重合体であることが好ましい。
成分（Ａ）の分子量分布Ｍｗ／量Ｍｎ（Ｑ値）は、好ましくは２〜２０、より好ましくは３〜１０の範囲である。Ｑ値が２未満であると、成形条件の幅が狭くなり成形性が劣ったものとなる。Ｑ値が２０を超えると、製造コストが高く工業的に実用的でないとのデメリットがでる。
The polypropylene resin as the component (A) is preferably a propylene homopolymer having the following physical properties.
The molecular weight distribution Mw / amount Mn (Q value) of the component (A) is preferably in the range of 2 to 20, more preferably 3 to 10. When the Q value is less than 2, the width of the molding condition becomes narrow and the moldability becomes inferior. When the Q value exceeds 20, there is a demerit that the production cost is high and not industrially practical.
成分（Ａ）のメルトフローレート（ＭＦＲ）は、樹脂温２３０℃、荷重２１．１８Ｎで測定された値であり、３０〜６００ｇ／１０分の範囲であることが好ましい。特に６０〜３００g／１０分が好ましい。ＭＦＲが３０ｇ／１０分未満であると、樹脂が繊維間に含浸し難くなる上、ペレット全体の流動性が低下し、射出成形し難くなる恐れがある。ＭＦＲが６００ｇ／１０分を超えると、ペレットの機械強度、耐熱性が低下する。 The melt flow rate (MFR) of the component (A) is a value measured at a resin temperature of 230 ° C. and a load of 21.18 N, and is preferably in the range of 30 to 600 g / 10 minutes. 60 to 300 g / 10 min is particularly preferable. If the MFR is less than 30 g / 10 minutes, the resin is less likely to be impregnated between the fibers, and the fluidity of the whole pellet is lowered, which may make injection molding difficult. If the MFR exceeds 600 g / 10 min, the mechanical strength and heat resistance of the pellet will be reduced.
成分（Ａ）の立体規則性指標（ｍｍｍｍ分率）は、９５％以上、好ましくは９７％以上である。ここで、ｍｍｍｍ分率とは、分子鎖中のペンタッド単位でのアイソタクチック分率を表し、同位体炭素核磁気共鳴分光（１３Ｃ−ＮＭＲ）法で求めた数値である。この方法は、特開平２００３−２２６７９１号公報［００１４］項に記載されている。ｍｍｍｍ分率が高いことは、結晶化度が高くなりやすく、高機械的強度、耐熱性が良好になりやすいことを意味する。ｍｍｍｍ分率が９５％未満であると、ペレットの機械強度、耐熱性が不十分な場合がある。ここでプロピレン系ブロック共重合体の場合は、ポリプロピレン部の立体規則性を示す。 The stereoregularity index (mmmm fraction) of the component (A) is 95% or more, preferably 97% or more. Here, the mmmm fraction represents an isotactic fraction in a pentad unit in a molecular chain, and is a numerical value determined by isotope carbon nuclear magnetic resonance spectroscopy ( 13 C-NMR). This method is described in Japanese Unexamined Patent Publication No. 2003-226791 [0014]. A high mmmm fraction means that the degree of crystallinity tends to be high, and high mechanical strength and heat resistance are likely to be good. If the mmmm fraction is less than 95%, the mechanical strength and heat resistance of the pellet may be insufficient. Here, in the case of a propylene-based block copolymer, the stereoregularity of the polypropylene portion is shown.
上記（Ｂ）成分は、繊維と樹脂との間に強固に結合した界面を構成するために必要である。（Ｂ）成分のＴｃは、９０〜１２５℃、好ましくは９５〜１２０℃、特に好ましくは１０５〜１１５℃の範囲であることが必要である。（Ｂ）成分の酸変性ポリオレフィンのＴｃが９０℃未満であると、トランスクリスタル層の発達が遅れ、強度が上がらず、１２５℃を超えると、繊維と樹脂との界面の柔軟性が失われ、樹脂の収縮時に発生する界面での応力を緩和できず、強度が低下する。また、（Ｂ）成分の結晶化が遅すぎると、繊維表面でのトランスクリスタル層が発達し難くなるため、（Ａ），（Ｂ）成分のＴｃの差、即ち「（Ａ）成分のＴｃ−（Ｂ）成分のＴｃ」が２０以下であることが好ましく、特に１５以下が好ましい。 The component (B) is necessary for constituting an interface firmly bonded between the fiber and the resin. Tc of (B) component needs to be 90-125 degreeC, Preferably it is 95-120 degreeC, Most preferably, it is the range of 105-115 degreeC. If the Tc of the component (B) acid-modified polyolefin is less than 90 ° C, the development of the transcrystal layer is delayed and the strength does not increase, and if it exceeds 125 ° C, the flexibility of the interface between the fiber and the resin is lost. The stress at the interface generated when the resin shrinks cannot be relieved, and the strength decreases. Further, if the crystallization of the component (B) is too slow, it becomes difficult to develop a transcrystal layer on the fiber surface. Therefore, the difference in Tc between the components (A) and (B), that is, “Tc− of the component (A)” (T) of component (B) is preferably 20 or less, particularly preferably 15 or less.
成分（Ｂ）の酸変性ポリオレフィンを製造するために用いるカルボン酸化合物又はその誘導体の具体例としては、例えば、マレイン酸、マレイン酸無水物、アクリル酸、メタクリル酸、ナジック酸、無水ナジック酸、フマル酸、イタコン酸、無水イタコン酸などが挙げられ、マレイン酸及びマレイン酸無水物が好ましい。 Specific examples of the carboxylic acid compound or derivative thereof used to produce the component (B) acid-modified polyolefin include, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, nadic acid, nadic anhydride, and fumaric acid. Examples thereof include acid, itaconic acid, itaconic anhydride and the like, and maleic acid and maleic anhydride are preferred.
成分（Ｂ）の酸変性ポリオレフィンは、下記物性を有する酸変性プロピレン重合体であることが好ましい。 The component (B) acid-modified polyolefin is preferably an acid-modified propylene polymer having the following physical properties.
成分（Ｂ）の極限粘度（η）は、０．１〜１．６ｄｌ／ｇ、好ましくは０．３〜１．０ｄｌ／ｇ、特に好ましくは、０．５〜０．８ｄｌ／ｇの範囲である。ここで、極限粘度（η）は、１３５℃−デリカン溶液で測定することができる。極限粘度（η）が０．１ｄｌ／ｇ未満であると、ペレットの機械強度、耐熱性が不十分な場合があり、また、変性時には通常化酸化物を使用するため、１．６ｄｌ／ｇを超えるような分子量の大きい酸変性プロピレン重合体は、製造が難しい。また、作れても変性率が低いことが多く、その結果、成分（Ｂ）を長繊維化ポリプロピレン系樹脂ペレット中に多量に配合しなければならない場合があり、コスト高になる。 The intrinsic viscosity (η) of the component (B) is 0.1 to 1.6 dl / g, preferably 0.3 to 1.0 dl / g, particularly preferably 0.5 to 0.8 dl / g. is there. Here, the intrinsic viscosity (η) can be measured with a 135 ° C.-delican solution. When the intrinsic viscosity (η) is less than 0.1 dl / g, the mechanical strength and heat resistance of the pellet may be insufficient, and since a normalized oxide is used during modification, 1.6 dl / g is required. Such an acid-modified propylene polymer having a large molecular weight is difficult to produce. Moreover, even if it is made, the modification rate is often low, and as a result, the component (B) may have to be blended in a large amount in the long-fibered polypropylene resin pellets, resulting in an increase in cost.
成分（Ｂ）の酸付加量（すなわち、酸変性ポリオレフィンの変性率）は、０．２〜１４質量％、好ましくは０．６〜１０質量％、特に好ましくは０．８〜６質量％の範囲である。酸付加量が０．２質量％未満であると、酸変性プロピレン重合体を多量に配合しないと、その配合の効果が現れず、不都合である。１４質量％を超えるような酸変性プロピレン重合体は、分子量が小さすぎて得られるペレットの強度特性が低下する恐れがある。 The acid addition amount of the component (B) (that is, the modification rate of the acid-modified polyolefin) is in the range of 0.2 to 14% by mass, preferably 0.6 to 10% by mass, particularly preferably 0.8 to 6% by mass. It is. If the acid addition amount is less than 0.2% by mass, the blending effect does not appear unless a large amount of the acid-modified propylene polymer is blended. If the acid-modified propylene polymer exceeds 14% by mass, the strength characteristics of the pellets obtained when the molecular weight is too small may decrease.
上記（Ｃ）成分の繊維は、５〜２０μｍの範囲の繊維径を有する。好ましくは、１０〜１８μｍである。繊維径が細いほどアスペクト比が向上し、強度を向上させやすくなるが、５μｍ未満の繊維は、製造コストが高くなり、一般用途においては経済的に不利となる。また、繊維が折れやすくなり、逆に強度が低下する場合もある。繊維系が２０μｍを超えると、アスペクト比が下がりすぎ、強度が十分に発現しない。 The fiber of the said (C) component has a fiber diameter of the range of 5-20 micrometers. Preferably, it is 10-18 micrometers. As the fiber diameter is thinner, the aspect ratio is improved and the strength is easily improved. However, a fiber having a diameter of less than 5 μm has a high production cost and is economically disadvantageous for general use. In addition, the fiber is likely to break, and the strength may decrease. When the fiber system exceeds 20 μm, the aspect ratio is too low and the strength is not sufficiently developed.
（Ｃ）成分の繊維としては、ガラス繊維、炭素繊維などの無機繊維、シリコン繊維、シリコン・チタン・炭素繊維、ボロン繊維、チタンなどの金属繊維、アラミド繊維、ポリエステル繊維、ポリアミド繊維、ビニロンなどの有機合成繊維、絹、綿、麻などの天然繊維などを用いることができる。これらは単独でも、２種以上を組み合わせたものでもよい。 (C) Component fibers include glass fibers, carbon fibers and other inorganic fibers, silicon fibers, silicon / titanium / carbon fibers, boron fibers, titanium and other metal fibers, aramid fibers, polyester fibers, polyamide fibers, vinylon, etc. Organic synthetic fibers, natural fibers such as silk, cotton and hemp can be used. These may be used alone or in combination of two or more.
上記（Ｃ）成分の繊維を処理するのに用いる収束剤には、カップリング剤及びフィルム・フォーマーが含まれている。カップリング剤は、繊維と樹脂との間に強固に結合した界面を構成するために必要である。フィルム・フォーマーは、製造工程上、繊維を束ねる為に必要である。収束剤で処理されていない繊維を用いた場合、樹脂が繊維中に含浸し難い上、得られたペレットの物性も低下する。 The sizing agent used to treat the fiber of component (C) includes a coupling agent and a film former. The coupling agent is necessary to form a strongly bonded interface between the fiber and the resin. A film former is necessary for bundling fibers during the manufacturing process. When fibers that have not been treated with a sizing agent are used, it is difficult for the resin to impregnate the fibers, and the physical properties of the resulting pellets are also reduced.
収束剤としては、公知のものを用いることができる。例えば、特開平８−９０６５９号公報、又は特開平１−３１９４３６号公報に記載の、アミノシラン、エポキシシランなどのカップリング剤、ウレタン系、オレフィン系、エポキシ系、酢酸ビニル系などのフィルム・フォーマーが挙げられる。
フィルム・フォーマーとしてのオレフィン系樹脂の具体例としては、塩素化又はクロロスルホン化されたポリオレフィン、不飽和カルボン酸で変性された変性オレフィンなどが挙げられる。特にマイレン酸及びマイレン酸無水物変性ポリプロピレンが好ましい。
また、カップリング剤及びフィルム・フォーマーなどの付着量（強熱減量）は０．１〜０．８質量％が好ましい。０．１質量％より少ないと収束効果が得られ難く、０．８質量％より多いと樹脂が開繊し難くなる。
A well-known thing can be used as a sizing agent. For example, there are coupling agents such as aminosilane and epoxysilane, urethane-based, olefin-based, epoxy-based, vinyl acetate-based film formers described in JP-A-8-90659 or JP-A-1-319436. Can be mentioned.
Specific examples of the olefin-based resin as the film former include chlorinated or chlorosulfonated polyolefin, modified olefin modified with unsaturated carboxylic acid, and the like. In particular, maleic acid and maleic anhydride-modified polypropylene are preferred.
Moreover, 0.1-0.8 mass% is preferable for the adhesion amount (ignition loss), such as a coupling agent and a film former. When the amount is less than 0.1% by mass, it is difficult to obtain a convergence effect, and when it is more than 0.8% by mass, the resin is difficult to open.
（Ｃ）成分の繊維はガラス繊維であることが好ましく、カップリング剤としてアミノシランカップリング剤を含み、フィルム・フォーマーとしてオレフィン系樹脂を含む収束剤によって処理されていることがより好ましい。 The fiber of component (C) is preferably a glass fiber, more preferably treated with a sizing agent containing an aminosilane coupling agent as a coupling agent and an olefinic resin as a film former.
本発明のペレットは、特開平１０−２６４１５２号公報に記載の方法に準じる方法やその他の公知の方法に従って製造することができる。 The pellet of the present invention can be produced according to a method according to the method described in JP-A-10-264152 or other known methods.
本発明のペレットは、本発明の目的及び効果を損なわない範囲内で上記の構成成分以外の成分を含んでいてもよい。このような成分としては、例えば、酸化防止剤、光安定剤、紫外線吸収剤、帯電防止剤、カーボンブラック、アルカリ土類金属化合物、硫化亜鉛、金属不活性剤などが挙げられる。 The pellet of this invention may contain components other than said structural component in the range which does not impair the objective and effect of this invention. Examples of such components include antioxidants, light stabilizers, ultraviolet absorbers, antistatic agents, carbon black, alkaline earth metal compounds, zinc sulfide, and metal deactivators.
本発明の第２の態様である長繊維強化樹脂ブレンド組成物（以下、本発明のブレンド組成物という）は、上記本発明の第１の態様であるペレットと、（Ｄ）プロピレン単独重合体及び／又はプロピレン系ブロック共重合体とをブレンドしてなることを特徴とする。 The long fiber reinforced resin blend composition (hereinafter referred to as the blend composition of the present invention) according to the second aspect of the present invention comprises the pellet according to the first aspect of the present invention, (D) a propylene homopolymer, and It is characterized by being blended with / and a propylene-based block copolymer.
上記（Ｄ）成分のプロピレン単独重合体及び／又はプロピレン系ブロック共重合体は、ガラス繊維量を任意量に調整するための希釈用樹脂である。（Ｄ）成分は、希釈用樹脂としてランダムプロピレン重合体を用いる場合に比べ、長繊維強化樹脂ペレットの剛性、耐熱性を低下させない点で優れている。 The propylene homopolymer and / or propylene-based block copolymer as the component (D) is a dilution resin for adjusting the glass fiber amount to an arbitrary amount. The component (D) is superior in that the rigidity and heat resistance of the long fiber reinforced resin pellets are not lowered as compared with the case where a random propylene polymer is used as the dilution resin.
（Ｄ）成分のプロピレン単独重合体としては、（Ａ）成分と同様なポリプロピレンが、高強度、耐熱性をよくする上で好ましい。ＭＦＲ（ＭＩ［ＰＰ］）は２〜６００ｇ／１０分が好ましい。３０〜１５０ｇ／１０分が特に好ましい。ＭＦＲが２未満であると、長繊維強化ポリプロピレン系樹脂ペレットと十分に分散せず、物性が低下する場合がある。また、６００を超えるとじん性が低下するとともにペレット化が困難でコストアップとなる。 As the propylene homopolymer of the component (D), the same polypropylene as the component (A) is preferable for improving high strength and heat resistance. MFR (MI [PP]) is preferably 2 to 600 g / 10 min. 30 to 150 g / 10 min is particularly preferred. If the MFR is less than 2, it may not be sufficiently dispersed with the long fiber reinforced polypropylene resin pellets, and physical properties may deteriorate. On the other hand, if it exceeds 600, toughness is lowered and pelletization is difficult, resulting in an increase in cost.
（Ｄ）成分のプロピレン系ブロック共重合体の具体例としては、例えば、Ｊ−３０５４ＨＰ（ＭＦＲ＝３０）、Ｊ−６０８３ＨＰ（ＭＦＲ＝６０）（共に出光石油化学（株）製）などが挙げられる。 Specific examples of the propylene block copolymer (D) include, for example, J-3054HP (MFR = 30), J-6083HP (MFR = 60) (both manufactured by Idemitsu Petrochemical Co., Ltd.), and the like. .
本発明のペレットと（Ｄ）成分との配合割合は、５：９５〜９５：５、好ましくは４０：６０〜９０：１０の範囲である。 The blending ratio of the pellet of the present invention and the component (D) is in the range of 5:95 to 95: 5, preferably 40:60 to 90:10.
本発明のブレンド組成物には、さらに、エラストマー、エラストマーとポリオレフィンとを任意の割合で溶融混合したもの、発泡剤、カーボンブラックや硫化亜鉛等の色材及び／又は添加剤（例えば、酸化防止剤、紫外線吸収剤、金属不活性化剤、潤滑剤など）を含むポリオレフィン、無機フィラー（例えば、タルク、マイカ、炭酸カルシウム、ミルドファイバーグラス、無機繊維、有機繊維）を含むポリオレフィンなどの１種又は２種以上をブレンドしてもよい。 The blend composition of the present invention further includes an elastomer, a material obtained by melt-mixing an elastomer and a polyolefin in an arbitrary ratio, a foaming agent, a color material such as carbon black and zinc sulfide, and / or an additive (for example, an antioxidant). 1 or 2 such as a polyolefin containing a UV absorber, a metal deactivator, a lubricant, etc., or a polyolefin containing an inorganic filler (eg, talc, mica, calcium carbonate, milled fiberglass, inorganic fiber, organic fiber). More than one seed may be blended.
本発明のペレットと（Ｄ）成分をブレンドする方法は特に限定されず、公知のいかなる方法を用いてもよい。 The method for blending the pellet of the present invention and the component (D) is not particularly limited, and any known method may be used.
本発明のブレンド組成物は、長繊維強化樹脂ブレンド組成物中の（Ａ）プロピレン重合体、又は（Ａ）プロピレン重合体及び（Ｂ）酸変性プロピレン重合体とを含むマトリックス樹脂、すなわち長繊維強化ポリプロピレン系樹脂ペレットの樹脂部、のメルトフローレートをＭＩ［ＭＢ］とし、（Ｄ）プロピレン単独重合体及び／又はプロピレン系ブロック共重合体のメルトフローレートをＭＩ［ＰＰ］とし、長繊維強化樹脂ブレンド組成物中の前記マトリックス樹脂の占める割合をαとしたときに下記関係式を満たすことが好ましい。
３０≦exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝≦２００
６０≦MI[MB]≦５００
特に好ましくは下記関係式を満たす。
７０≦exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝≦１６０
７０≦MI[MB]≦１６０
The blend composition of the present invention comprises (A) a propylene polymer in a long fiber reinforced resin blend composition, or a matrix resin containing (A) a propylene polymer and (B) an acid-modified propylene polymer, that is, a long fiber reinforced resin. The melt flow rate of the resin part of the polypropylene resin pellet is MI [MB], and (D) the melt flow rate of the propylene homopolymer and / or propylene block copolymer is MI [PP]. It is preferable that the following relational expression is satisfied when the ratio of the matrix resin in the blend composition is α.
30 ≦ exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])} ≦ 200
60 ≦ MI [MB] ≦ 500
Particularly preferably, the following relational expression is satisfied.
70 ≦ exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])} ≦ 160
70 ≦ MI [MB] ≦ 160
上記式中、exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝は、長繊維強化樹脂ペレットと長繊維強化樹脂ブレンド組成物とを合わせた、樹脂部全体の粘性の指標であり、分子量と対応する。これが３０未満の場合には、大型成形品の成形が困難となり、２００を超えると樹脂部の靭性が失われる。
また、ブレンド物全体のガラス量は３０〜５０重量％が好ましく，３５〜４５重量％が特に好ましい。３５重量％以下では剛性が不足し、４５重量％以上ではガラスの分散が不充分な場合がある。
In the above formula, exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])} is a combination of the long fiber reinforced resin pellet and the long fiber reinforced resin blend composition. It is an index of the viscosity of the entire resin part and corresponds to the molecular weight. When this is less than 30, it becomes difficult to mold a large molded product, and when it exceeds 200, the toughness of the resin part is lost.
Moreover, 30-50 weight% is preferable and the glass amount of the whole blend is especially preferable 35-45 weight%. If it is 35% by weight or less, the rigidity is insufficient, and if it is 45% by weight or more, the dispersion of the glass may be insufficient.
本発明の第３の態様である成形体（以下、本発明の成形体という）は、上記本発明の第１の態様のペレット又は上記本発明の第２の態様のブレンド組成物を成形してなる成形体であって、成形後に残存する繊維の重量平均繊維長が１ｍｍ以上、好ましくは１．８ｍｍ以上であることを特徴とする。 The molded body according to the third aspect of the present invention (hereinafter referred to as the molded body of the present invention) is formed by molding the pellet of the first aspect of the present invention or the blend composition of the second aspect of the present invention. The weight average fiber length of the fibers remaining after the molding is 1 mm or more, preferably 1.8 mm or more.
ここで、成形後に残存する繊維の重量平均繊維長は、特開平２００２−２２０５３８号公報に記載の方法によって測定することができる。この重量平均繊維長が成形後において１ｍｍ未満であると、繊維量の割には、成形体の機械物性、耐熱性等の向上度が低いというデメリットがある。 Here, the weight average fiber length of the fibers remaining after molding can be measured by the method described in JP-A No. 2002-220538. If this weight average fiber length is less than 1 mm after molding, there is a demerit that the degree of improvement in mechanical properties, heat resistance, etc. of the molded product is low for the amount of fiber.
本発明の成形体の成形方法は、特に限定されず、目的とする成形品に応じて公知のいずれかの方法を選択すればよい。例えば、射出成形法、押出成形法、中空成形法、圧縮成形法、射出圧縮成形法、膨張成形法（ＩＥＭ）などが挙げられる。 The molding method of the molded body of the present invention is not particularly limited, and any known method may be selected according to the target molded product. Examples thereof include an injection molding method, an extrusion molding method, a hollow molding method, a compression molding method, an injection compression molding method, and an expansion molding method (IEM).
本発明の成形体は、従来の長繊維強化樹脂成形体に比べて強度に優れており、より高い強度を要求される用途、例えば、自動車部品（フロントエンド、クーリングファン、エンジンアンダーカバー、エンジンカバー、ラジエターボックス、サイドドア、バックドアインナー、バックドアアウター、外板、ルーフレール、ドアハンドル、ラゲージボックス、ホイールカバー、ハンドルステップなど）、自動二輪・自転車部品（ラゲージボックス、ハンドル、ホイールなど）、住宅関連部品（温水洗浄便座部品、浴室部品、椅子の脚、バルブ類、メーターボックスなど）、その他（電動工具部品、草刈り機ハンドル、ホースジョイント、トレイなど）にも適用できるものである。特に高い強度が要求される自動車部品（フロントエンド、ステップなど）に有効である。フロントエンドには、シュラウドモジュール、ファンシュラウド又はクーリングモジュールが含まれる。 The molded product of the present invention is superior in strength to conventional long fiber reinforced resin molded products, and uses such as automotive parts (front end, cooling fan, engine under cover, engine cover) that require higher strength. , Radiator box, side door, back door inner, back door outer, outer plate, roof rail, door handle, luggage box, wheel cover, handle step, etc.), motorcycle and bicycle parts (luggage box, handle, wheel, etc.), housing It can also be applied to related parts (hot water flush toilet parts, bathroom parts, chair legs, valves, meter boxes, etc.) and other parts (power tool parts, mower handles, hose joints, trays, etc.). This is particularly effective for automobile parts (front end, step, etc.) that require high strength. The front end includes a shroud module, a fan shroud or a cooling module.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
＜材料及び方法＞
（Ａ）成分：下記表１に記載の物性を有するプロピレン単独重合体（ＰＰ−Ａ〜Ｈ）を用意した。
<Materials and methods>
Component (A): Propylene homopolymers (PP-A to H) having physical properties described in Table 1 below were prepared.
（Ｂ）成分：下記表２に記載の物性を有する無水マレイン酸変性プロピレン重合体（ＭＰＰ−Ａ〜Ｅ）を用意した。 Component (B): Maleic anhydride-modified propylene polymers (MPP-AE) having the physical properties described in Table 2 below were prepared.
（Ｃ）成分：収束剤で処理した繊維径１３μｍ（商品名：ＥＲ７４０ 旭ファイバーグラス（株））及び１６μｍ（商品名：ＥＲ２２２０ 旭ファイバーグラス（株））の２種類のガラス繊維（旭ファイバーグラス（株）製）を用意した。 Component (C): Fiber diameter of 13 μm (trade name: ER740 Asahi Fiber Glass Co., Ltd.) and 16 μm (trade name: ER2220 Asahi Fiber Glass Co., Ltd.) treated with a sizing agent. Co., Ltd.) was prepared.
（Ｄ）成分：希釈樹脂として、下記表３に記載の物性を有するプロピレン単独重合体（ＰＰ−Ｌ〜Ｎ）を用意した。 Component (D): Propylene homopolymers (PP-L to N) having physical properties described in Table 3 below were prepared as dilution resins.
上記表１〜３中の物性値は、それぞれ下記の方法により測定した。
（１）結晶化温度（Ｔｃ）
機器名：ＤＳＣ７（パーキンエルマー社製）を用いた示差走査熱量計（ＤＳＣ）測定法によって測定した。結晶化温度（Ｔｃ）は、２２０℃で５分間保持した後、２２０℃から３０℃まで２０℃／分で降温し、得られた曲線からピーク頂点を求めた。ＤＳＣ曲線の読み方、結晶化温度の求め方は、ＪＩＳ Ｋ ７１２１に準じた。
The physical property values in the above Tables 1 to 3 were measured by the following methods, respectively.
(1) Crystallization temperature (Tc)
Device name: Measured by a differential scanning calorimeter (DSC) measurement method using DSC7 (manufactured by Perkin Elmer). The crystallization temperature (Tc) was maintained at 220 ° C. for 5 minutes, then the temperature was decreased from 220 ° C. to 30 ° C. at 20 ° C./min, and the peak vertex was obtained from the obtained curve. The method for reading the DSC curve and the method for obtaining the crystallization temperature were in accordance with JIS K7121.
（２）分子量分布Ｍｗ／Ｍｎ（Ｑ値）
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を下記装置及び条件で行い、測定した。
（ＧＰＣ測定装置）
カラム：ＴＯＳＯＧＭＨＨＲ−Ｈ（Ｓ）ＨＴ
検出器：液体クロマトグラム用ＲＩ検出器 ＷＡＴＥＲＳ １５０Ｃ
（測定条件）
溶媒：１，２，４−トリクロロベンゼン
温度：１４５℃
流速：１．０ミリリットル
試料濃度：２．２ｍｇ／ミリリットル
注入量：１６０マイクロリットル
検量線：Ｕｎｉｖｅｓａｌ Ｃａｌｉｂｒａｔｉｏｎ
解析プログラム：ＨＴ−ＧＰＣ（Ｖｅｒ．１．０）
(2) Molecular weight distribution Mw / Mn (Q value)
Gel permeation chromatography (GPC) was performed with the following apparatus and conditions.
(GPC measuring device)
Column: TOSOGMMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
(Measurement condition)
Solvent: 1,2,4-trichlorobenzene Temperature: 145 ° C
Flow rate: 1.0 ml Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
（３）メルトフローレート（ＭＦＲ）
樹脂温２３０℃、荷重２１．１８Ｎで測定した。
(3) Melt flow rate (MFR)
The measurement was performed at a resin temperature of 230 ° C. and a load of 21.18 N.
（４）立体規則性指標（ｍｍｍｍ分率）
重合体を１，２，４−トリクロロベンゼンと重ベンゼンの９０：１０（容量比）混合溶液に溶解し、１３Ｃ−ＮＭＲ（日本電子（株）製、商品名：ＬＡ−５００）を用いて、１３０℃でプロトン完全デカップリング法により測定した。
(4) Stereoregularity index (mmmm fraction)
The polymer was dissolved in a 90:10 (volume ratio) mixed solution of 1,2,4-trichlorobenzene and heavy benzene, and 13 C-NMR (trade name: LA-500, manufactured by JEOL Ltd.) was used. , Measured at 130 ° C. by the proton complete decoupling method.
（５）極限粘度（η）
テトラリン中、１３５℃で測定した。
(5) Intrinsic viscosity (η)
Measurements were made at 135 ° C. in tetralin.
（６）酸付加量
以下の方法で測定した。
（ｉ）ドデシルコハク酸と濃度調整用のポリプロピレンパウダー（商品名：Ｈ７００ 出光石油化学（株））を用いて、ピーク面積とマレイン酸量との関係式を算出して検量線とした。
（ii）試料から、２３０℃の熱プレスにより、１０分予熱後、４分間加圧（５ＭＰａ）、冷却プレスにより３分間加圧（５ＭＰａ）を行ない、厚みが０．１ｍｍ程度のフィルムを作成した。
（iii）フィルムをメチルエチルケトン（ＭＥＫ）にて６５℃３時間で洗浄後、１１０℃で２時間真空乾燥した。
（iv）乾燥後２時間以内に、フィルムのＦＴ−ＩＲ透過スペクトルを測定し、ＦＴ−ＩＲスペクトルの１６７０〜１８１０ｃｍ−１のピーク面積を計算し、（ｉ）の検量線と比較してマレイン酸付加量を求めた。
(6) Acid addition amount It measured with the following method.
(I) Using dodecylsuccinic acid and a polypropylene powder for adjusting the concentration (trade name: H700, Idemitsu Petrochemical Co., Ltd.), a relational expression between the peak area and the amount of maleic acid was calculated and used as a calibration curve.
(Ii) A film having a thickness of about 0.1 mm was prepared from the sample by preheating for 10 minutes at 230 ° C. with pressure, pressing for 4 minutes (5 MPa), and pressing for 3 minutes with a cooling press (5 MPa). .
(Iii) The film was washed with methyl ethyl ketone (MEK) at 65 ° C. for 3 hours and then vacuum-dried at 110 ° C. for 2 hours.
(Iv) Within 2 hours after drying, the FT-IR transmission spectrum of the film was measured, the peak area of 1670-1810 cm −1 of the FT-IR spectrum was calculated, and maleic acid was compared with the calibration curve of (i) The additional amount was determined.
実施例１〜５，８〜１１、参考例１〜４、比較例１，２
（１）長繊維強化樹脂ペレットの製造
表１記載の特性を有する（Ａ）プロピレン単独重合体（ＰＰ−Ａ〜Ｈ）と、表２記載の特性を有する（Ｂ）マレイン酸変性プロピレン重合体（ＭＰＰ−Ａ〜Ｅ）とを、下記表４に示す割合で混合し、２８０℃で溶融して５０ｍφ押出機からダイ内の含浸槽へ供給した。次に、（Ｃ）ガラス繊維を約４０００本束ねたガラスロービングを、下記表４に記載の配合量で２８０℃に加熱された上記の溶融された樹脂が供給されている含浸槽へ導いた。含浸槽中には、１０本のロッド（直径１０ｍｍ）を直線状に配置した。供給速度を２０ｍ／分に調整しつつ２００℃で予熱したガラスロービングを含浸槽内に送り込み、槽内のロッドにかけて開繊し、溶融樹脂を含浸させ、含浸槽から引き出して冷却し、ペレタイザで切断して下記表４に示す長さのペレットを得た。得られたペレットは繊維が、ペレットの長手方向へ略平行に配列していた。
Examples 1 to 5, 8 to 11, Reference Examples 1 to 4, Comparative Examples 1 and 2
(1) Manufacture of long fiber reinforced resin pellets (A) Propylene homopolymer (PP-A to H) having the characteristics described in Table 1 and (B) Maleic acid-modified propylene polymer having the characteristics described in Table 2 ( MPP-A to E) were mixed at the ratio shown in Table 4 below, melted at 280 ° C., and supplied from the 50 mφ extruder to the impregnation tank in the die. Next, (C) A glass roving in which about 4000 glass fibers were bundled was introduced into an impregnation tank supplied with the above-mentioned molten resin heated to 280 ° C. in the blending amounts shown in Table 4 below. Ten rods (diameter 10 mm) were arranged linearly in the impregnation tank. Glass roving preheated at 200 ° C. while feeding rate is adjusted to 20 m / min is sent into the impregnation tank, opened on the rod in the tank, opened by impregnation with molten resin, cooled from the impregnation tank, and cut with a pelletizer. Thus, pellets having the lengths shown in Table 4 below were obtained. In the obtained pellet, the fibers were arranged substantially parallel to the longitudinal direction of the pellet.
得られたペレット（ＧＦＭＢ−１〜１５）のマトリックス樹脂部の結晶化温度（Ｔｃ）をＧＦＭＢから測定した。即ち、ＧＦＭＢの端をカッターで削り、削片（粉）を直接測定した。カルボン酸化合物又は誘導体の質量％は削片（粉）のＦＴ−ＩＲにより求めた。結果を下記表４に示す。 The crystallization temperature (Tc) of the matrix resin part of the obtained pellets (GFMB-1 to 15) was measured from GFMB. That is, the end of GFMB was shaved with a cutter, and the scrap (powder) was directly measured. The mass% of the carboxylic acid compound or derivative was determined by FT-IR of the scrap (powder). The results are shown in Table 4 below.
実施例１５〜１９，２２〜２６，２９，３０、参考例５〜１０、比較例３〜６
(１)長繊維強化樹脂ブレンド組成物の製造
上記表４に記載の組成を有するペレット（ＧＦＭＢ−１〜１５）と、上記表３に記載の（Ｄ）プロピレン単独重合体（ＰＰ−Ｌ〜Ｒ）を、それぞれ下記表５に記載の割合で混合して長繊維強化樹脂ブレンド組成物を製造した。なお、表５中、実施例１及び比較例１では、ペレットに（Ｄ）プロピレン単独重合体をブレンドせず、ペレットのままの組成とした。
Examples 15-19, 22-26, 29, 30, Reference Examples 5-10, Comparative Examples 3-6
(1) Production of long fiber reinforced resin blend composition Pellets (GFMB-1 to 15) having the composition described in Table 4 above and (D) propylene homopolymer (PP-LR) described in Table 3 above. ) Were mixed at the ratios shown in Table 5 below to produce long fiber reinforced resin blend compositions. In Table 5, in Example 1 and Comparative Example 1, (D) propylene homopolymer was not blended with the pellets, and the pellets were kept as they were.
得られた各ブレンド組成物又はペレットの樹脂部全体のＭＦＲを、式
exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝
に従って算出した。算出結果を下記表５に示す。
MFR of the whole resin part of each blend composition or pellet obtained is expressed by the formula
exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])}
Calculated according to The calculation results are shown in Table 5 below.
(２)樹脂ブレンド成形品の強度特性評価
上記（１）で製造した樹脂ブレンドから、ＪＩＳ Ｋ ７１５２−１：９９の多目的試験片をＪＩＳ Ｋ ６９２１：９７に従い成形し、試験片とした。これを下記試験で用いた。試験結果を下記表５に示す。
(2) Strength characteristic evaluation of resin blend molded article From the resin blend produced in the above (1), a multipurpose test piece of JIS K 7152-1: 99 was molded in accordance with JIS K 6921: 97 to obtain a test piece. This was used in the following test. The test results are shown in Table 5 below.
各物性試験の方法は以下の通りである。
（ａ）引張り破断強度（ＪＩＳ Ｋ ７１６１及び７１６２）
（ｂ）曲げ強度（ＪＩＳ Ｋ ７１７１）
（ｃ）曲げ弾性率（ＪＩＳ Ｋ ７１７１）
（ｄ）シャルピー衝撃強度（ＪＩＳ Ｋ ７１７１、２３℃、ノッチ有り、ノッチ無し）
（ｅ）成形体中の重量平均繊維長：（ｄ）の試験片を灰化した後、画像処理機（ルーゼックス社製）に取り込んで測定した。
The method of each physical property test is as follows.
(A) Tensile strength at break (JIS K 7161 and 7162)
(B) Bending strength (JIS K 7171)
(C) Flexural modulus (JIS K 7171)
(D) Charpy impact strength (JIS K 7171, 23 ° C., with notch, without notch)
(E) Weight average fiber length in the molded body: After the test piece of (d) was incinerated, it was taken into an image processor (manufactured by Luzex) and measured.
exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝
に従って算出した値（ＭＦＲ計算値）である。
exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])}
(MFR calculated value).
表５を見ると、曲げ弾性率が同等であり、（Ａ）成分のｍｍｍｍ分率が同じである参考例５と比較例３は、同程度の剛性及び強度を有すると予測されるにもかかわらず、実際には、比較例３では引張り強度及びシャルピー衝撃強度が劣っていることがわかる。すなわち、マトリックス樹脂（（Ａ）成分と（Ｂ）成分とからなる）の結晶化温度（Ｔｃ）が１２０℃を超えている比較例１に比べ、結晶化温度（Ｔｃ）がトランスクリスタル層が十分に発達しうる温度である実施例１では、強度特性が向上することがわかる。 Table 5 shows that Reference Example 5 and Comparative Example 3 having the same bending elastic modulus and the same mmmm fraction of the component (A) are expected to have the same degree of rigidity and strength. In fact, it can be seen that Comparative Example 3 is inferior in tensile strength and Charpy impact strength. That is, the crystallization temperature (Tc) of the matrix resin (consisting of the component (A) and the component (B)) exceeds 120 ° C., and the crystallization temperature (Tc) is sufficient in the transcrystal layer. It can be seen that the strength characteristics are improved in Example 1, which is a temperature that can be developed to a high level.
本発明によれば、樹脂部の結晶化温度がトランスクリスタル層発現温度より低い樹脂を用いることにより、長繊維強化樹脂成形体の強度を飛躍的に向上させ、より高い強度が要求される用途への適用が可能となる。 According to the present invention, by using a resin in which the crystallization temperature of the resin portion is lower than the transcrystal layer expression temperature, the strength of the long fiber reinforced resin molded product is dramatically improved, and the application requiring higher strength is required. Can be applied.
本発明によれば、ガラス繊維の配合量が４０質量％時において、引張り破壊強度１５０ＭＰａ以上（従来品では１２０〜１４０ＭＰａ）、曲げ強さ２３０ＭＰａ以上（従来品では１９０〜２２０ＭＰａ）、かつ、シャルピー衝撃強度（２３℃、ノッチ無し）８０ＫＪ／ｍ２以上（従来品では５０〜７０ＫＪ／ｍ２）の成形体が得られる。 According to the present invention, when the compounding amount of the glass fiber is 40% by mass, the tensile fracture strength is 150 MPa or more (120 to 140 MPa in the conventional product), the bending strength is 230 MPa or more (190 to 220 MPa in the conventional product), and the Charpy impact strength (23 ° C., unnotched) molding of 80 kJ / m 2 or more (in the conventional 50~70KJ / m 2) is obtained.
本発明の長繊維強化ポリプロピレン系樹脂ペレット及び長繊維強化樹脂ブレンド組成物は、強度が高く、自動車部品、自動二輪・自転車部品、住宅関連部品などに幅広く使用できる。 The long fiber reinforced polypropylene resin pellet and the long fiber reinforced resin blend composition of the present invention have high strength and can be widely used for automobile parts, motorcycle / bicycle parts, house-related parts and the like.
Claims (8)
（Ｄ）プロピレン単独重合体及び／又はプロピレン系ブロック共重合体とを、ガラス量が３５〜５０重量％となるように、ブレンドしてなる長繊維強化樹脂ブレンド組成物。
（Ａ）メルトフローレート（ＭＦＲ；２３０℃、２１．１８Ｎ）が３０〜３００ｇ／１０分であり、ＤＳＣ測定法で測定した結晶化温度（Ｔｃ）が１１０〜１１８℃のポリプロピレン系樹脂 １０〜６９．９質量％
（Ｂ）ＤＳＣ測定法で測定した結晶化温度（Ｔｃ）が１０５〜１１５℃であって、「（Ａ）成分のＴｃ−（Ｂ）成分のＴｃ」が１５以下であり、
極限粘度（η）が０．５〜１．６ｄｌ／ｇであり、酸付加量が０．６〜１０質量％のカルボン酸化合物又はその誘導体によって変性されたポリオレフィン ０．１〜２０質量％
（Ｃ）カップリング剤及びフィルム・フォーマーを含む収束剤で処理された繊維径５〜２０μｍのガラス繊維 ４０〜７０質量％ A long fiber reinforced polypropylene resin having a crystallization temperature (Tc) of 110 to 118 ° C. of a resin matrix portion measured by a differential scanning calorimeter (DSC) measurement method, comprising the following components (A), (B) and (C) Pellets,
(D) A long fiber reinforced resin blend composition obtained by blending a propylene homopolymer and / or a propylene-based block copolymer so that the glass amount is 35 to 50% by weight .
(A) Polypropylene resin having a melt flow rate (MFR; 230 ° C., 21.18 N) of 30 to 300 g / 10 minutes and a crystallization temperature (Tc) measured by DSC measurement method of 110 to 118 ° C. .9% by mass
(B) The crystallization temperature (Tc) measured by the DSC measurement method is 105 to 115 ° C., and “Tc of component (A) —Tc of component (B)” is 15 or less,
Polyolefin modified with a carboxylic acid compound or derivative thereof having an intrinsic viscosity (η) of 0.5 to 1.6 dl / g and an acid addition amount of 0.6 to 10 mass% 0.1 to 20 mass%
(C) 40 to 70% by mass of glass fiber having a fiber diameter of 5 to 20 μm treated with a sizing agent including a coupling agent and a film former.
（Ａ）分子量分布Ｍｗ／Ｍｎ（Ｑ値）が２〜２０であり、同位体炭素核磁気共鳴分光（１３Ｃ−ＮＭＲ）法で求めた立体規則性指標（ｍｍｍｍ分率）が９５％以上のプロピレン重合体
（Ｃ）カップリング剤としてアミノシランカップリング剤を含み、フィルム・フォーマーとしてオレフィン系樹脂を含む収束剤によって処理されたガラス繊維 The said fiber (A) and (C) have the following physical property, The long fiber reinforced resin blend composition in any one of Claims 1-3 characterized by the above-mentioned.
(A) The molecular weight distribution Mw / Mn (Q value) is 2 to 20, and the stereoregularity index (mmmm fraction) determined by isotope carbon nuclear magnetic resonance spectroscopy ( 13 C-NMR) is 95% or more. Glass fiber treated with a sizing agent containing an aminosilane coupling agent as a propylene polymer (C) coupling agent and an olefinic resin as a film former
３０≦exp｛α×ln(MI[MB])＋(１−α)×ln(MI[PP])｝≦２００
６０≦MI[MB]≦５００ The melt flow rate of the matrix resin containing (A) the propylene polymer or (A) the propylene polymer and (B) the acid-modified propylene polymer in the long fiber reinforced resin blend composition is MI [MB], and (D ) When the melt flow rate of the propylene homopolymer and / or the propylene block copolymer is MI [PP], and the ratio of the matrix resin in the long fiber reinforced resin blend composition is α, the following relational expression is obtained. The long fiber reinforced resin blend composition according to claim 1, wherein the long fiber reinforced resin blend composition is satisfied.
30 ≦ exp {α × ln (MI [MB]) + (1−α) × ln (MI [PP])} ≦ 200
60 ≦ MI [MB] ≦ 500
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| JP2008150416A (en) * | 2006-12-14 | 2008-07-03 | Kuraray Co Ltd | Lightweight fiber-reinforced resin composition excellent in impact resistance and molded article comprising the same |
| JP2009120714A (en) * | 2007-11-14 | 2009-06-04 | Idemitsu Kosan Co Ltd | Composite resin pellet, molded article and method for producing composite resin pellet |
| CN101925639B (en) | 2008-01-24 | 2013-05-22 | 住友化学株式会社 | Surface-treated fiber, resin composition, and molded article of composition |
| EP2927265A4 (en) * | 2012-11-30 | 2016-02-24 | Mitsubishi Rayon Co | Pellet mixture, carbon fiber-reinforced polypropylene resin composition, molded body, and method for producing pellet mixture |
| WO2016076411A1 (en) * | 2014-11-13 | 2016-05-19 | 三井化学株式会社 | Carbon fiber-reinforced resin composition and molded article produced from same |
| KR101674609B1 (en) * | 2015-05-07 | 2016-11-09 | 롯데케미칼 주식회사 | Preparing method of polyolefin resin mono chip and polyolefin resin mono chip |
| WO2017003070A1 (en) | 2015-06-29 | 2017-01-05 | 롯데케미칼 주식회사 | Polyolefin resin, preparation method therefor, and vehicle rear bumper beam using same |
| KR102124702B1 (en) * | 2018-11-14 | 2020-06-19 | 한화토탈 주식회사 | Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom |
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